Mineralogy at the extremes

 Thomas S. Duffy 

Nature volume 451, pages269–270(2008)Cite this article

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The discovery of a new silicate structure at conditions corresponding to a
depth of 2,700 kilometres below Earth's surface has fundamentally
changed our understanding of the boundary between the core and
mantle.
Connections between scientific disciplines can emerge in unexpected ways. In
2004, mineralogists rushed to their libraries to locate a somewhat obscure 40-
year-old paper1 that described an unusual crystal structure found in a
compound of calcium iridium oxide (CaIrO3). The reason for the sudden
geological interest in the iridate family was the discovery that
(Mg,Fe)SiO3 perovskite — the major mineral in Earth's vast lower mantle —
adopted this same structure when subjected to pressures of more than 125 GPa
(1.25 million bars) and temperatures above 2,000 K in the laboratory 2,3. Under
these crushing pressures and searing temperatures, Earth's mantle finally
divulged one of its deepest secrets. The new structure, commonly referred to
as post-perovskite, is composed of layers of SiO 6 octahedra sharing edges and
corners to form sheets interleaved with layers of larger Mg and Fe cations
(Fig. 1). Although mineralogists had speculated over the years that perovskite
might undergo some kind of transformation at high pressures, the formation of
this CaIrO3-type structure had been wholly unanticipated by theory and
experiment.

Figure 1: Crystal structure of the post-perovskite phase of (Mg,Fe)SiO 3.

The structure consists of layers of linked silicon octahedra (yellow). Red
spheres at vertices of SiO  octahedra are oxygen ions, and blue spheres are
6

magnesium and iron ions.

Full size image

New view of the deep Earth

Earth's lower mantle, which extends from a depth of 660 km to 2,890 km, is
the largest region of Earth, with a mass that is roughly 100 times that of the
crust. Understanding the mineralogical constituents of this region is vital to
unravelling Earth's origin, evolution and dynamic behaviour (see page 261).
Without any way to sample it directly, our fuzzy picture of the lower mantle
comes mainly from seismic studies, and most of the region seems to be fairly
homogeneous. However, a puzzling aspect has been a thin layer extending
about 200 km above the boundary between the core and the mantle (known
for historical reasons as D″) that has several anomalous properties 4. The D″
region is separated from the rest of the mantle by a discontinuity in seismic
velocity. Compared with the rest of the lower mantle, the D″ region is very
heterogeneous and has increased anisotropy of seismic waves (see page 266).
Complexity in the deepest mantle should not be surprising. The hot but solid
silicate minerals of the mantle are juxtaposed against the churning liquid iron
core. The region is a likely source for the hot plumes that reach all the way to
Earth's surface, as well as perhaps the final repository for subducting slabs
from Earth's surface.
So what has been learned about the connection between D″ and post-
perovskite in the three years since its discovery? On balance, many of post-
perovskite's characteristics match those predicted by seismic observations of
D″ (ref. 5). Although it is difficult to measure pressure accurately under such
extreme conditions in the laboratory, the transformation seems to occur at
pressures corresponding to those found at the top of the D″ region. More
importantly, the strongly positive pressure–temperature, or Clapeyron, slope
of the transition means that the transformation occurs deeper in locally hotter
regions and shallower in cooler regions, which is consistent with seismic
observations. But it can be much more complex than this. Earth has a steep
thermal gradient near the core–mantle boundary, and temperatures at the base
of the mantle might become hot enough for perovskite to re-emerge just above
the core6. In this case, complex structures such as localized lenses of post-
perovskite could be expected (Fig. 2). Attempts to image the structures in this
region seismically have already yielded some tantalizing results 7,8.

Figure 2: Cross-section through Earth's interior showing the expected

range of pressures and temperatures.
a, The lower mantle extends from a depth of 660 km to a depth of 2,890 km,
with the D″ region extending about 200 km above the core. b, A simplified
diagram of possible structures of the D″ region near the core–mantle boundary
(the region indicated by dashed lines in a)6.
 Full size image

Going beyond the core–mantle boundary

Are there more discoveries of the magnitude of post-perovskite awaiting us in
the deep Earth? The answer to this question is almost certainly yes. Several
trends are fuelling a vibrant and vigorous research enterprise in the
exploration of deep planetary interiors and the wider high-pressure realm. In
the laboratory, sustained pressures in excess of 1 Mbar (relevant to Earth's
deep mantle and core) can be achieved with a diamond anvil cell. However,
mineralogists are now finding that they can carry out increasingly reliable
studies under extreme conditions without experimental input, by using
computer calculations based on quantum-mechanical principles, such as
density-functional theory9. The major advantage of such methods is that they
can simulate pressure conditions of 1 Mbar nearly as easily as they can
simulate 1 bar. The disadvantage is that the theory's inherent approximations
mean that the results have to be compared with experiments. Theoretical
studies have provided tremendous insights into post-perovskite — confirming
its thermodynamic stability and providing predictions of the Clapeyron slopes,
seismic anisotropies and other key properties, some of which have yet to be
confirmed experimentally. Rapid improvements in theoretical methods and
their applications to increasingly complex systems will certainly be a major
driving force for the field in the coming years.
In laboratory studies carried out at high pressures, the megabar era has now
been entered. Pressures above 1 Mbar (100 GPa), which until recently were
the domain of a determined few, are now just the starting point for much
forefront science. Pressures in Earth's interior range up to 360 GPa, and
temperatures are perhaps 5,500–6,000 K near Earth's centre. Much of the deep
mantle and core thus remain terra incognita from an experimental
perspective. To progress, a coupled effort is required to achieve and sustain a
well-characterized pressure–temperature state while making sophisticated
measurements of a range of key physical variables on both solid and liquid
phases, including structure, elasticity, bonding, transport properties, lattice
dynamics, electrical and magnetic properties and chemical interactions among
increasingly complex geological assemblages.
Key questions about Earth's core (which has a pressure range of 135–360
GPa) include the identity of its main light elements, the nature of melting and
iron-rich liquids at core conditions, core–mantle interactions and the origin of
the solid inner core's seismic anisotropy. Moreover, Earth cannot be studied in
isolation. The interior structures of the giant planets present a myriad of
fascinating questions, and their study requires even higher pressures and
temperatures. For giant planets, the materials of main interest are the
fundamental ices and gases (for example, hydrogen, water and methane) of
the Solar System. Complexity abounds in these constituents, and new bonding
configurations, structural changes and metallization are all expected 10. Such
studies can provide the answers to basic questions about the mechanisms of
planetary formation and the origin of magnetic fields. Even further, new
possibilities can be envisaged for the structures of hot 'Jupiters' and possible
super 'Earths' and super 'Ganymedes' in solar systems beyond that of Earth,
offering combinations of composition, pressures and temperatures that hold
the promise of further surprises.
Scaling up
Aside from the scientific opportunities, a key driving force for mineral physics
has been the union of high-pressure experiments with synchrotron X-ray
facilities11. High-pressure studies are especially well positioned to benefit
from the combination of high-energy and high-intensity radiation that
synchrotrons specialize in delivering. X-ray spectroscopy techniques that have
matured at synchrotrons have found important applications in the Earth
sciences. The discovery that iron in mantle minerals transforms from a high-
spin (or unpaired) state to a low-spin (or paired) state is another finding of
great importance12. The change in spin state is accompanied by changes in
partitioning behaviour, compressibility and optical properties, all of which can
strongly affect the behaviour of the lower mantle. This is a reminder that
mineral properties can change markedly under extreme conditions even
without any accompanying changes in crystal structure.
Synchrotrons are now focal points around which communities of high-
pressure scientists nucleate. The result has been a flowering of
interdisciplinary interactions. This trend towards community facilities
promises to grow as new opportunities abound to bring high-pressure mineral
physics to neutron facilities such as the Spallation Neutron Source at Oak
Ridge, Tennessee, and laser facilities such as the National Ignition Facility in
Livermore, California. It is worth emphasizing that static techniques are only
one method of achieving ultra-high pressure–temperature conditions.
Historically, high pressures were first reached by shock-wave methods that
sustain extreme conditions for no longer than a microsecond. Dynamic
methods are also undergoing a renaissance driven by new capabilities in high-
powered lasers. These techniques are achieving multi-megabar conditions, and
there is potential to reach much greater pressures by using these methods
alone or together with diamond anvil technologies 13.
The discovery of post-perovskite is likely to be remembered as a turning point
in understanding the structure and dynamics of the deep Earth. But the
elucidation of the connections between the geophysics of the deep Earth and
its mineralogical constituents has only just begun. Given the fundamental
questions that remain to be addressed, the unexplored territory of pressure–
temperature–composition space and newly emerging scientific capabilities,
post-perovskite promises to be just the first of many scientific highlights that
will characterize the megabar realm of deep planetary interiors.

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Acknowledgements
G. Shen (Carnegie Institution of Washington) and S.-H. Shim (Massachusetts
Institute of Technology) provided helpful comments.

Author information
Affiliations
1. Thomas S. Duffy is in the Department of Geosciences, Princeton
University, Princeton, New Jersey 08544, USA.
Thomas S. Duffy

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